TWI490316B - Ester group containing liquid crystals for optical or electro optical devices - Google Patents

Description

Ester-containing liquid crystal for optical or optoelectronic components

The present invention relates to a polymerizable liquid crystal compound (I) and a composition thereof and a polymer which are used for preparing a birefringent layer for an optical or photovoltaic element.

Birefringent layers are used to fabricate optical or optoelectronic components such as waveguides, optical gratings, filters, phase retardation films, rotators, piezoelectric cells, and nonlinear optical cells and films. The choice of liquid crystal compound for use with any of the foregoing optical or optoelectronic components depends on its associated optical properties, such as optical anisotropy, refractive index, transparency, and dispersion.

The birefringent layer can be produced, for example, by orienting a layer containing a liquid crystal compound.

If the liquid crystal is polymerisable, the applied configuration of the alignment layer on the liquid crystal compound can be stabilized, and accordingly, a polymer network can be formed to allow a fixed orientation. The resulting birefringent layer has a high viscosity and is stable to mechanical stress, temperature and exposure.

The desired one is a polymerizable liquid crystal compound which exhibits stability to chemical, thermal or electromagnetic radiation. Moreover, good manufacturing characteristics derived from the polymerizable liquid crystal compound are desirable, for example, simple and economical availability. Further, it is advantageous to have a polymerizable liquid crystal compound having good application characteristics such as good adhesion, solubility, and miscibility with other polymerizable liquid crystal compounds, and over a wide temperature range - for example, 25 to 80 ° C, Advantageously, the liquid crystal phase(s) are extended from 25 to 150 °C.

There is a need for a further polymerizable liquid crystal compound which exhibits a wide range of liquid crystal heat and which is capable of imparting a polymerizable liquid crystal compound or mixture on a substrate to a polymer network. The way to maintain stability throughout the entire period - preferably before the interconnection - is oriented on the substrate. Moreover, these polymerizable liquid crystal compounds should be economical and easy to obtain and exhibit good application characteristics.

The present invention relates to a liquid crystal compound (I) having a liquid crystal phase:

Wherein R ¹ and R ² are independently of each other a group having the formula (Ia)

Wherein: "----", a broken line, representing a bond to the compound (I), and wherein -(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² - Is a divalent core, wherein; C ¹ and C ^{3 are,} in each case, independently substituted or unsubstituted non-aromatic, aromatic, carbocyclic or heterocyclic groups, and C ² is one. a non-aromatic, aromatic, carbocyclic or heterocyclic group which is unsubstituted or substituted by an unbranched hydrocarbon group consisting of 1 to 20 C atoms, wherein one or more C atoms, The -CH- or -CH ₂ - group is unsubstituted, or wherein one or more C atoms, -CH- or -CH ₂ - groups are bonded to a hetero atom, such as -O-, -S-, -NH-, -N(CH ₃ )-substitution, or substitution by a displacement group selected from the group consisting of -N=N-, -CO-C=C-, -CH (OH)-, -CO-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O(CO)-, -O(CO ) -O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -CH=CH- and -C≡C-, provided that the oxygen atoms are not directly linked to each other; X ¹ and X ^{The 2} series independently represent -O-, -S-, -NH-, -N(CH ₃ )-, -N=N-, -CH=N-, -N=CH-, -CO -C=C-, -CH(OH)-, -CO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -OCF ₂ -, -COO-, -O(CO)-, -O(CO)-O-, -S-CO-, -CO-S-, - SOO-, -OSO-, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C Or a single bond; n ¹ and n ² are integers, each independently having a value of 0, 1, 2, 3, 4, preferably 1, and SP ¹ represents a non-aromatic or aromatic, carbocyclic ring. Or a heterocyclyl group, or a CH=CH- group, a C≡C-group or a branched or unbranched C ₃ -C ₂₄ -alkylene group, one or more of which The C atom, the -CH- or -CH ₂ - group is unsubstituted, or wherein one or more C atoms, -CH- or -CH ₂ - groups are selected from a hetero atom or at least one selected from Substituting a single displacement group of the following group: -N=N-, -CO-C=C-, CO-, -CH ₂ (CO)-, -SO-, -CH(SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O(CO)-, -O(CO)-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, OCH ₂ -, -CH ₂ O-, -CH=CH-, and -C≡C-; provided that the oxygen atoms are not directly linked to each other; more preferably SP ¹ represents a CH=CH- group (cis or trans), a C≡C- group or a substituted or unsubstituted C ₃ -C ₁₂ alkyl group, most preferably C ₃ -C ₆ alkyl, especially n-propyl, n-butyl, n-pentyl, n-hexyl, wherein one or more C atoms, -CH- or -CH ₂ - groups are not replaced, or one of them A plurality of C atoms, -CH- or -CH ₂ - groups are replaced by -O- or -S-, or at least one single CH=CH- group (cis or trans); provided that the oxygen atoms are each other Not directly linked; SP ² represents a substituted or unsubstituted spacer; preferably SP ² represents a non-aromatic or aromatic, carbocyclic or heterocyclic group, or branched or un a branched C ₁ -C ₂₄ -alkylene group in which one or more C atoms, -CH- or -CH ₂ - groups are unsubstituted, or one or more C atoms, -CH The - or -CH ₂ - group is replaced by a hetero atom or at least a single displacement group selected from the group consisting of -N=N-, -CO-C=C-, CO- , -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O(CO)-, -O(CO )-O-, -S-CO- -CO-S -, - SOO - , - OSO-, OCH 2 -, - CH 2 O -, - CH = CH-, and -C≡C-; the proviso that oxygen atoms are not directly coupled; is more preferably SP ² represents a substituted or unsubstituted C ₁ -C ₁₂ alkylene group, most preferably a C ₁ -C ₆ alkylene group, especially a methylene group, an extended ethyl group, a n-propyl group, a n-butyl group. a pentyl group or a hexyl group, wherein one or more C atoms, -CH- or -CH ₂ - groups are unsubstituted, or one or more C atoms, -CH- or -CH ₂ - groups The group is replaced by a hetero atom or at least one single displacement group selected from the group consisting of -N=N-, -CO-C=C-, CO-, -CH ₂ (CO) -, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O(CO)-, -O(CO)-O-, -S -CO-, -CO-S-, -SOO-, -OSO-, OCH ₂ -, -CH ₂ O-, -CH=CH-, and -C≡C-; provided that the oxygen atoms are not directly coupled to each other; Particularly preferred is that the SP ² represents an unsubstituted C ₁ -C ₆ alkyl, methylene, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl group, one or more of which The C atom, the -CH- or -CH ₂ - group is not substituted, or One or more C atoms, -CH- or -CH ₂ - groups are replaced by -O- or -S-, or at least one single CH=CH- group; provided that the oxygen atoms are not directly linked to each other; P is a polymerizable group.

Further preferred is the compound (I) in which the SP ¹ and the Sp ² systems are different from each other.

In the context of the present invention: - Halogen has the meaning of fluorine, chlorine, bromine, and iodine, preferably fluorine and chlorine; -CH=CH- has the corresponding meaning of a cis or trans group; The substituent is preferably halogen, aryl, cycloalkyl, amine, cyano, epoxy, hydroxy, nitro, pendant oxy, alkyl, alkoxy, C ₁ -C ₂₀ -alkoxycarbonyl , alkylcarbonyloxy, alkylcarbonyl, alkylcarbonylamino; - the term alkyl as used in a single word or in combination or in conjunction with other terms, for example, C ₁ -C ₂₄ alkane a group, preferably a C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₆ alkyl group, which is substituted, unsubstituted, branched, unbranched, unsubstituted, or one or more of The C atom may be replaced by a hetero atom such as -O-, -S-, -N(CH ₃ )- or a substitution group selected from the group consisting of -N=N-, -CO -C=C-, -CO-, -CH ₂ (CO)-, -SO-, -CH ₂ (SO)-, -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O (CO)-, -O(CO)-O-, -S-CO-, -CO-S-, -SOO-, -OSO-, -CH ₂ -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CH=CH-, -C≡C-, and single bond; preference is Base, ethyl, propyl, isopropyl, n-butyl, isobutyl, isopentyl, n-pentyl, n-hexyl, isohexyl, or substituted by -O-, -COO-, -OCO-; The term "alkyl" is a diradical derivative of an alkyl group in which the alkyl group has the above meaning and preference; the alkoxy group is an -O-alkyl derivative and the alkoxycarbonyl group is -COO- The alkyl derivative, the term alkylcarbonyloxy is the -OCO-alkyl derivative, the alkylcarbonyl group is the OC-alkyl derivative, and the alkylcarbonylamino group is the HNOC-alkyl derivative. The alkyl group has the meaning and preference given above, the term "aryl" is the residue of the aromatic group; the term "cycloalkyl" is a non-aromatic, carbocyclic, or heterocyclic group. Residue;- The term hydrocarbon includes straight-chain and branched alkyl, alkylene, alkenyl, alkenyl, alkenyl, and alkynyl; - non-aromatic term includes carbocyclic or heterocyclic The group - the term aromatic includes a carbocyclic or heterocyclic group which is a single ring; two adjacent monocyclic rings composed of five or six atoms; consisting of eight, nine or ten atoms Double loop system; or by thirteen Tricyclic ring system consisting of fourteen atoms; Preferably, the term "aromatic" means comprise five, six, ten or 14 ring atoms, such as furyl, phenyl or phenylene, pyridine, tris a pyrimidine, naphthalene, phenanthrene, biphenyl or extended triphenyl or tetrahydronaphthalene unit interrupted uninterrupted or by at least one single hetero atom and/or at least one single bridging group; preferred aromatic group The group is benzene, phenyl, biphenyl or terphenyl and the most preferred is phenyl; preferably the aromatic, carbocyclic or heterocyclic group - for example - unsubstituted or Preferred substituents by mono or polysubstituted; carbocyclic or heterocyclic aromatic groups are at least one polar group and/or monoalkyl, acryloyloxy, alkylpropenyloxy, alkane Oxyl, alkylcarbonyloxy, alkyloxycarbonyloxy, alkyl-oxycarbonyloxy, methacryloxy, vinyl, vinyloxy and/or allyloxy Preferred polar group is nitro, halogen, hydroxy; cyano or carboxyl group; - the term phenyl or phenyl - when used in the context of the present invention - preferably represents a situation A 1,2-, 1,3- or 1,4-phenylene or phenyl group substituted. Preferably, the phenyl group is a 1,3- or 1,4-(extended) phenyl group. A 1,4-(extended) phenyl group is especially preferred.

Preferably, C ¹ and C ³ are selected from:

and

Wherein: L represents hydrogen, halogen; C ₁ -C ₂₄ -alkyl, preferably methyl, ethyl, n-butyl, n-hexyl; C ₁ -C ₂₄ -alkoxy, C ₁ -C ₂₄ - Alkoxycarbonyl, C ₁ -C ₂₄ -alkylcarbonyloxy, C ₁ -C ₂₄ -alkylcarbonyl, preferably -COCH ₃ ; cyano, C ₁ -C ₂₄ -alkylcarbonylamino; -NO ₂ , r ¹ is 0, 1, ₂ , 3, or 4, r ² is 0, 1, 2, or 3, and r ³ is 0, 1, 2.

More preferably, the C ¹ and C ³ systems are selected from the group consisting of the following compounds:

Wherein L represents hydrogen, halogen, methyl, ethyl, propyl, butyl, pentyl, hexyl; C ₁ -C ₆ -alkoxy, -COCH ₃ nitrile, or -NO ₂ ,r ¹ ,r ² And r ³ are independently 0 or 1 from each other.

Preferably, the C ² is selected from the non-preferable group C ² ' of the compound shown below:

And the palmitic group C ² "" of the compound shown below:

Wherein: L represents hydrogen, an unbranched hydrocarbon group consisting of 1 to 6 C atoms, wherein one or more C atoms, -CH- or -CH ₂ - groups are not substituted, or one of them Or a plurality of C atoms, -CH- or -CH ₂ - groups are replaced by one of -O-, -S-, -NH-, -N(CH ₃ )-, or one selected from Substituted by a replacement group of the following group: -N=N-, -CO-C=C-, -CH(OH)-, -CO-, -SO-, -CH ₂ (SO)- , -SO ₂ -, -CH ₂ (SO ₂ )-, -COO-, -O(CO)-, -O(CO)-O-, -S-CO-, -CO-S-, -SOO- , -OSO-, -CH=CH-, and -C≡C-, provided that the oxygen atoms are not directly bonded to each other; preferably one or more of the C atoms, -CH- or -CH ₂ - groups Not replaced, or replaced by -O-, or -COO-, -O(CO)-, -O(CO)-O; more preferably L is hydrogen, methyl, ethyl, propyl, A The oxy group is most preferably hydrogen or methyl, ethyl or methoxy, and particularly preferably hydrogen or methyl; s ¹ is 0, 1, 2, 3, or 4, and s ² is 0, 1 2, 3 or 3, s ³ is 0, 1, or 2, and s ⁴ is 0 or 1; and it is preferred that s ¹ , s ² , and s ⁴ are independently 0 or 1 from each other.

More preferably, the C ² moiety is selected from the non-preferable group C ² ' of the compound shown below:

And the palmitic group C ² "" of the compound shown below:

Wherein L, s ¹ , and s ² have the same meanings and preferences as explained above.

Most preferably, the C ² moiety is selected from the non-preferable group C ² ' of the compound shown below:

And the palm group C ² ” shown below: as well as Wherein L, s ¹ , s ² , and s ⁴ have the same meanings and preferences as explained above.

Moreover, more preferred is a compound (I) wherein P is CH ₂ =CZ ¹ -COO-,

Wherein k is an integer from 1 to 20; or P is HO-CZ ² Z ³ -, HS-CZ ² Z ³ , HZ ² N-, CH ² = CZ ¹ -CO-NH-; CH ₂ = CZ ² - ( O) _k1 -, where k1 is 0 or 1; CH ₃ -CHCH-O-, (CH ₂ CH) ₂ CH-OCO-, (CH ₂ CH-CH ₂ ) ₂ CH-OCO, (CH ₂ =CH) ₂ CH-O-, (CH ₂ =CH-CH ₂ ) ₂ N-, (CH ₂ =CH-CH ₂ ) ₂ N-CO-, or Z ⁴ Z ⁵ Z ⁶ Si-, wherein Z ¹ is H, Cl, CN, phenyl, or C ₁ -C ₆ alkyl, the Z ² and Z ³ systems are each independently H or C ₁ -C ₆ alkyl, and the Z ⁴ , Z ⁵ , and Z ⁶ systems are independently Ground is Cl, with 1 to 6 C atoms Alkyl or Carbonylalkyl.

Preferably, P is CH ₂ =CZ ¹ -COO-

Wherein Z ¹ and Z ² are each independently H or a C ₁ -C ₆ alkyl group, preferably H or a methyl group and K is an integer of 1 to 6, preferably 1.

More preferably, P is CH ₂ =CZ ¹ -COO-, wherein Z ¹ is H, or a C ₁ -C ₆ alkyl group, which is especially methyl.

Further, more preferred is a compound of formula (II):

Wherein C ² , R ¹ , L, r ¹ , n ¹ , n ² have the meanings and preferences as given above; and especially preferred is compound (II) wherein C ² is 1, 4:3 , 6-di-dehydrate-2,5-dideoxy-2,5-dimethyl-D-mannitol, 1,4:3,6-dide-D-mannitol, 1,4 :3,6-di-dehydrate-2,5-dideoxy-2,5-dimethyl-D-glucitol, 1,4:3,6-di-sorbitan-2,5-di a methyl-ether or a 1,4-phenylene group which is unsubstituted or substituted with an unbranched C ₁ -C ₆ -alkyl group, wherein one or more C atoms, -CH- Or the -CH ₂ - group is unsubstituted or substituted by -O-, -CO-, -COO-, -O(CO)-, or -O(CO)-O-, provided that the oxygen atoms are in each other Not directly coupled, and; R ¹ , L, r ¹ have the meanings and preferences as given above; and more preferably where r ¹ is zero.

Especially preferred are compounds of formula (IV):

Wherein SP ¹ , SP ² , and L have the same meaning and preference as explained above, and Z is hydrogen or methyl.

Moreover, more preferred is a compound (I) having an adhesion of >4, preferably greater than >5.

Adhesion values are based on an average of 2 tests (one by 180° with respect to the substrate and then with a 90° pull) and are classified as follows:

5- 0% of the area is removed

4- Less than 10% of the area is removed

3- 10-30% of the area is removed

2- 30-50% of the area is removed

1- More than 50% of the area is removed

* The removed area is the release area of the sample, which is adhered with an adhesive tape, which is then attempted to be pulled at 180° and 90°.

The adhesion value is generated by the following standard procedure: First, a surface region comprising a sample of Compound (I) (produced according to the application of the present invention/Example 7) is selected, the region being free of defects, for example, for example, Scratches or dust, and the area is 1-2 cm away from the edge. Adhesive tape (Nichiban Adhesive Tape) is then oriented perpendicular to the direction of the linearly polarized light used to orient the orientation layer (25 ° C (+/- 2 ° C) and 50% (+/- 10%) humidity) Paste and firmly adhere to the surface of the crystal lattice, then let stand for 1 min waiting time. After this waiting time, the adhesive tape was quickly removed by first pulling the substrate at 180° and then pulling the substrate at 90°.

A further embodiment of the invention relates to a liquid crystal composition comprising at least one compound of formula (I) and optionally another polymerizable liquid crystal compound and/or additive.

Polymerizable liquid crystal compounds are those which are well known in the art, especially preferred and incorporated by reference herein to the following polymerizable liquid crystal compounds: WO 2005/105932, WO 2005/054406, WO 2004/ 085547, WO 2003/027056, US 2004/0164272, US 6,746,729, US 6,733,690, WO 2000/48985, WO 2000/07975, WO 2000/04110, WO 2000/05189, WO 99/37735, US 6395351, US 5700393, US 5851424, and US 5650534.

More preferred is a liquid crystal composition comprising at least one compound of formula (I) wherein C ² is selected from the group consisting of a non-preferable group C ² ' falling within the meaning and preferences given above.

Moreover, more preferred is a liquid crystal composition comprising: a compound of formula (I) wherein C ² is selected from the group consisting of a non-preferable group C ² ' falling within the meaning given above. And at least one single compound of formula (I), wherein C ² is a pair of palm groups selected from groups C ² " falling within the meaning and preferences given above; or an inclusion A composition having at least two different compounds of formula (I) with C ² .

Furthermore, it is more preferred that the liquid crystal composition comprises at least one compound (I) and at least one compound (III)

Wherein C ² , C ² ”, R ¹ , L, r ¹ , n ¹ , n ² have the meanings and preferences as given above.

Moreover, it is more preferred that the liquid crystal composition comprises at least one single compound (I) and three compounds (V), (VI) and (VII)

Wherein R ¹ , L, and r ¹ have the meanings and preferences given above.

The amount of the components in the liquid crystal composition depends on the intended use. In the case where a liquid crystal composition is desired, the amount of the components in the composition of the present invention is limited by the liquid crystal phase of the composition which must be retained. Conventionally, the compound (I) with or without the palm group C ² has an amount of from 0.1 to 99% by weight, preferably from 1 to 50% by weight, even more preferably from 1 to 30% by weight of the composition. A portion by weight and especially preferably even more preferably from 1 to 10% by weight, provided that the sum of the weight percentages of all components of the mixture is 100.

Still preferably, the liquid crystal composition of the present invention comprises

a) 0.1 to 99.1% by weight of the compound (I), wherein C ² is C ² ',

b) 0.1 to 99.1% by weight of the palm compound (I), wherein C ² is C ² ""

Wherein C ^2, C ² ', and C ² "system having the meanings and preferences given above and wherein the sum of the weight percent of all component is 100; Preferably, the chiral component (I) based accounting The composition is used in an amount of 0.1 to 20% by weight.

Further, it is preferred that the liquid crystal composition of the present invention contains the compound (I) and a reactive or non-reactive palm compound. Reactive and non-reactive palmate compounds are known in the art and are described in U.S. Patent No. 5,798,147, the disclosure of which is incorporated herein by reference.

Most preferred is a liquid crystal composition comprising a compound of formula (I) as well as other ingredients such as, for example, additives, solvents.

Commonly used additives are antioxidants, initiators (such as photoinitiators), accelerators, dyes, inhibitors, activators, fillers, chain transfer inhibitors, pigments, antistatic agents, flame retardants, thickening Agents, shakers, surfactants, viscosity modifiers, extenders, plasticizers, adhesives, catalysts, sensitizers, stabilizers (for example, such as phenol derivatives, such as 4-ethoxyphenol or 2 , 6-bis-tertiary-butyl-4-methylphenol (BHT), a lubricant; a dispersing agent; a polymerizable binder and/or a monomeric compound which can be converted into a polymerizable binder by polymerization, Alternatively, in the case of emulsion coatings and printing inks, dispersion aids are disclosed, for example, in U.S. Patent No. 5,798,147; hydrophobic agents, adhesives, glidants, defoamers, deaerators, diluents, adjuvants , colorants, dyes and pigments, curing inhibitors, such as hydroquinone, p-tert-butyl catechol; 2,6-bis-tertiary-butyl-p-methylphenol; N-phenyl-2-naphthylamine; or a photo-orientable monomer or oligomer or polymer as described in EP 1 090 325 B; the amount of the additive in the composition is subject to the composition of the invention which must be retained The required limits for the liquid crystal phase. Conventionally, the reactive or non-reactive additive has an amount of from 0.01 to 50% by weight, preferably from 1 to 30% by weight, even more preferably from 1 to 10% by weight, based on the composition.

If the composition of the present invention contains a stabilizer, the latter is generally present in an amount of from 0.01 to 5% by weight, preferably from 0.1 to 1% by weight, based on the total amount of the composition.

The starter is applied in an amount effective to initiate the curing of the composition. The effective portion depends on the method parameters and the starting material characteristics. Usually, the amount is between 0.01 and 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. Combinations of two or more starters (light- or hot starters) can also be employed.

The liquid crystal composition of the present invention is a solid or diluted in a solvent of an organic solvent and/or water, such as a solution, a gel, a dispersion, or an emulsion.

Preferably, the composition is a clear solution. The solvent or solvent mixture used in the present application may be any compound capable of dissolving the liquid crystal composition according to the present invention. At least one solvent can be used, such as a common polar solvent or a non-polar solvent. Particularly preferred solvents are those which enable the material solution to have good coatability or printability to the substrate to be coated.

Most preferably, the liquid crystal composition comprises a compound of formula (I) and a non-polar solvent.

The non-polar solvent is a compound having a low dielectric constant and cannot be miscible with water, and for example, preferred are hexane, benzene, toluene, diethyl ether, 1,4-two. Alkane, tetrahydrofuran (THF), chloroform, ethyl acetate, dichloromethane, 1,3-dioxolane (DXG), and more preferably 1,3-dioxolane (DXG).

Polar solvents are aprotic or protic.

Most preferably, the liquid crystal composition comprises a compound of formula (I) and a polar solvent.

A polar aprotic solvent is a solvent that shares ionic solubility with a protic solvent but lacks acidic hydrogen. These solvents generally have a high dielectric constant and a high polarity. Preferred polar solvents are acetone, acetonitrile (MeCN), dimethylformamide (DMF), dimethyl hydrazine (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone , N-vinylpyrrolidone, γ-butyrolactone (BL), N-methylmorpholine, propylene diacetate, chlorobenzene, tetrahydrofuran, cyclopentanone (CP), methyl ethyl ketone (MEK , aniline (AN), cyclohexanone (CHN), methyl isobutyl ketone (MIBK), 1-methoxy-2-propyl acetate (MPA), and mixtures thereof.

The polar protic solvent is a solvent containing dissociable H+, such as hydrofluoric acid. The molecules of this type of solvent contribute to H+ (protons). Conversely, an aprotic solvent cannot contribute to hydrogen bonding. The common property of protic solvents is that they exhibit hydrogen bonding, have acidic hydrogen (although these may be extremely weak acids), and are capable of stabilizing ions (cations are paired by unpaired free electrons and anions are hydrogen bonded). Examples are acetic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, formic acid, 2-butoxyethanol (BC), ethyl carbitol, butyl carbitol, ethyl carbitol Acid esters, ethylene glycol, propylene glycol monoacetate, dipropylene glycol, dipropylene glycol monomethyl ether, and water.

Preferably, the organic solvent used in the present application is a protic or aprotic polar or non-polar solvent.

Preferred solvents are the following, but are not limited to: -ketones such as, for example, acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl Ketone (MEK), - guanamines, such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N-vinylpyrrole Pyridone, N,N-dimethylacetamide, -carbamate-ethers, such as tetrahydrofuran (THF), ethylene glycol, dipropylene glycol, butyl carbitol, ethyl carbitol acetic acid Esters, dipropylene glycol monomethyl ether, 1,3-dioxocyclopentane (DXG)-esters, such as ethyl acetate (EA), 1-methoxy-2-propyl acetate (MPA), γ-butyl Lactone (BL), propylene glycol monoacetate, propylene diacetate, -alcohols, such as 2-butoxyethanol (BC), ethyl cyproterone, butyl cycas, dimethyl Hydrazine (DMSO), a halogen hydrocarbon such as dichloromethane, chlorobenzene, a non-polar solvent such as, but not limited to, hydrocarbons such as hexane, heptane, toluene; aniline, petroleum ether, and the like mixture.

Preferred solvents are acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N-vinylpyrrolidone, N,N-dimethylacetamide, (AN), tetrahydrofuran (THF) , 1,3-dioxocyclopentane (DXG), ethylene glycol, dipropylene glycol, butyl carbitol, ethyl carbitol acetate, dipropylene glycol monomethyl ether, ethyl acetate (EA), acetic acid 1-Methoxy-2-propyl ester (MPA), γ-butyrolactone (BL), propylene glycol monoacetate, propylene diacetate, dipropylene glycol monomethyl ether, dimethyl hydrazine (DMSO).

The most preferred are cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), ethyl acetate (EA), 1-methoxy acetate. 2-propyl ester (MPA), 1,3-dioxocyclopentane (DXG), dimethyl alum (DMSO).

It may be advantageous to add a solvent depending on the intended use. The typical concentration of the composition disposed in the solvent is an active ingredient dissolved in the solvent - for example, the compound (I) and optionally the additive - is between 2 and 50% by weight, preferably between 10 and 40% by weight. between.

The compound (I) of the present invention can be produced by a method known in the art.

Moreover, the present invention also relates to a method for preparing an ester-containing compound, preferably a compound (I), which comprises

a) bringing a compound of formula (VIII)

P-Sp ² -OH (VIII)

Contact with a compound of formula (IX)

b) and the dihydroxy compound of formula (XI)

HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² -OH (XI);

Or a compound of formula (XII)

HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² -Y (XII)

Wherein P, Sp ² , Sp ¹ , C ¹ , C ² , C ³ , n ¹ , n ² have the same meaning as explained above, Z is hydrogen or methyl and Y represents COOH, COOC ₁ -C ₆ alkyl, halogen or CN, Y is preferably CN.

Preferably, steps a) and b) can be carried out "one-pot reaction", or the process can be carried out in more than one step by, for example, separating the intermediate formed in step a).

Preferably, the compounds are contacted by coupling them.

In general, the coupling in step a) can be carried out with or without a solvent. However, it may be advantageous to use a solvent such as a polar or non-polar aprotic solvent falling within the meaning of the solvent given below. Preferred solvents are tetrahydrofuran, toluene, xylene.

Process step b) is preferably carried out in the presence of a solvent, preferably an aprotic solvent.

Moreover, the coupling steps a) and b) can be carried out in the presence of the stabilizer 2,6-di-tertiary-butyl-4-methyl-phenol.

Preferably, step a) is carried out in the presence of a base, such as a tertiary amine.

The temperature of the coupling steps a) and b) depends on the reaction parameters, such as the reaction materials used.

Preferably, step a) is carried out by high temperatures, for example, from 30 to 180 °C.

Preferably, the molar ratio of the starting material of step a) is, for example, in the range of 1:0.8 to 0.8:1 and depends on the reactivity and solubility of the solvent used.

Preferably, the molar ratio of the dihydroxy (XI) to the compound obtained in step a) is, for example, in the range of (0.5:1 to 0.1:1); and the monohydroxy group of the formula (XII) The molar ratio of the compound to the compound obtained in step a) is, for example, in the range of (1:1 to 1:0.8).

The coupling of step b) of the compound obtained in step a) is preferably carried out by esterification of an activated carboxylic acid (for example, decyl chloride), or by coupling of carbodiimide, or by using a mixed acid anhydride. For example, methanesulfonate chloride is used. Preferably, step b) is carried out in the presence of DMAP or pyridine.

The mercapto chloride of the resulting compound of step a) can be carried out according to conventional methods for forming mercapto chlorides, such as those described in standard books. Furthermore, the carbodiimide coupling and reaction with the mixed anhydride can be illustrated by conventional methods in standard chemistry books.

The hydroxyalkyl acrylate is either commercially available or can be readily prepared by the reaction of, for example, acrylonitrile chloride and a dihydroxy compound.

Compound HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² -OH(XI) or HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² - C ³ ) _n ² -Y(XII) is conventional and can be synthesized according to literature methods (for example, JP 11080090). These can be prepared, for example, by or in a reaction similar to the dissolution of p-toluenesulfonic acid monohydrate in an aprotic solvent such as o-xylene, similar to 4-hydroxybenzoic acid and methylhydroquinone.

Yet another embodiment of the present invention is also directed to a method for preparing Compound (I), the method comprising

a) making the dihydroxy compound (XI),

HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² -OH(XI)

Or a monohydroxy compound of formula (XII),

HO-(C ¹ -X ¹ ) _n ¹ -C ² -(X ² -C ³ ) _n ² -Y(XII)

Coupling with a compound of formula (IX)

,as well as

b) Subsequently, the compound obtained in step a) is coupled with the following

P-Sp ² -OH (VIII)

Wherein P, SP ² , SP ¹ , C ¹ , C ² , C ³ , n ¹ , n ² , and Y have the meanings and preferences given above.

The reaction conditions and preferences of steps a) and b) are as described above in the preparation of the method of compound (I), provided that the starting materials are replaced and the molecular proportions are correspondingly changed.

Further, the present invention relates to a product obtained by the above method.

Moreover, the invention comprises a process for the preparation of an unpatterned or patterned birefringent layer comprising polymerizing a compound (I) or a composition according to the invention.

The invention also encompasses the use of a compound (I) or composition of the invention for the preparation of an unpatterned or patterned birefringent layer.

Preferably, the term "patterning" means birefringence patterning and/or thickness patterning and/or patterning of the optical axis, and/or patterning of the degree of polymerization and preferably comprises photopolymerization. The degree of birefringence represents the difference between the extraordinary and ordinary refractive indices.

The term "unpatterned" means that the entire area of the layer is bounded birefringent.

Moreover, the present invention encompasses a process for preparing a birefringent layer comprising, preferably on an aligned surface, polymerizing a compound (I) or composition of the invention.

For the purposes of the present invention, an alignment surface means any substrate surface that has the ability to be used for alignment of liquid crystals.

The substrate is, for example, a plastic such as PET, polyethylene terephthalate, or TAC, cellulose triacetate, or any other material that may optionally be coated with indium tin oxide (ITO). , for example, glass. Moreover, the substrate can comprise a coating that produces or delivers such alignment capabilities. Such coatings are well known as alignment layers.

The alignment layer can be prepared using any technique known in the art including, but not limited to, rubbing methods such as rubbed polyimine or polylysine; embossing, scratching, SiO or the like Oblique angle deposition method; yellow photolithography gate method, LB film (Langmuir Bodgett film), SAMS (self-assembled monolayer surface), ion irradiation method, laser exposure method of surface structure, alignment texture transfer by imprint The method of photoalignment includes, for example, photopolymerization, photopolymerization, photolysis, and photoisomerization.

A preferred alignment layer is a layer of photo-oriented photopolymer. To prepare the alignment layer, the composition of the present invention is coated on a substrate and photopolymerized. Photopolymerization means that the composition is cured using light, preferably UV light, and more preferably UVA- to obtain a crosslinked birefringent layer. The curing time depends on, inter alia, the reactivity of the polymerizable material, the thickness of the coating, the type of polymerization initiator and the power of the UV lamp. Preferred is a linear photopolymerization alignment layer. A preferred alignment surface is a PET and alignment layer, especially a photo alignment layer.

The invention also relates to a process for the preparation of a birefringent layer comprising a compound (I) or a composition according to the invention.

Preferably, the method for preparing a birefringent layer comprises

a) coating or printing the compound (I) or composition of the present invention on an alignment surface,

b) dry as appropriate, and

c) Subsequently, polymerization, preferably photopolymerization.

Generally, the composition is applied by conventional coating and printing methods well known in the art. The coating method includes, for example, a spin coating method, an air knife coating method, a knife coating method, a knife coating method, a reverse coating method, a transfer roll coating method, a gravure roll coating method, a contact roll coating method, Cast coating method, spray coating method, slot coating method, calender coating method, electrodeposition coating method, dip coating method, or extrusion coating method.

Printing methods include, for example, relief printing methods such as elastic relief printing; inkjet printing; engraving gravure printing, such as direct gravure or offset gravure; and lithography, such as offset printing; Or solder paste printing, such as screen printing.

Whether or not the drying step is carried out depends on the consistency of the composition. If the composition contains a solvent, the composition is usually dried after the coating step.

In general, "drying" includes, for example, the extraction of a solvent by means of a heated gas, which uses, for example, an air stream that convects heat and carries away solvent vapors (convection or direct). Drying method). Dry faster at higher temperatures. In addition, the quality of the product or film needs to be considered when determining the temperature to be applied for drying. Other possibilities are vacuum drying, in which the heat is supplied by contact conduction or radiation (or microwave) while the generated vapor is removed by a vacuum system; indirect or contact drying (heating through hot walls), such as rollers Drying method, vacuum drying method; high frequency drying method (radio frequency or microwave is absorbed into the interior of the material); freeze drying method or low pressure lyophilization method; mechanical solvent removal.

In a preferred embodiment of the invention, the process comprises photopolymerizing the compound (I) or composition obtained in step a) or b) of the coating. This photopolymerization is carried out by irradiation.

For the purposes of the present invention, the radiation is polarized or unpolarized. Preference is given to unpolarized light, but in special cases polarized or partially polarized, linear, circular or elliptical polarized light may also be applied.

Traditionally, lamps have been used for photopolymerization. The intensity of the lamp used for illumination should preferably be higher than 0,2 mW/cm ² , more preferably higher than 10 mW/cm ² , most preferably higher than 20 mW/cm ² , especially preferably higher than 50 mW/cm ² .

Photopolymerization can also be achieved by electron beam (EB).

The invention also relates to the use of unpatterned or patterned birefringent layers for optical or optoelectronic components and systems, especially multilayer systems, or components.

Moreover, the invention also relates to a method for preparing an optical or optoelectronic component and system, in particular a multilayer system, or an element comprising a cholesterol layer, and/or an unpatterned or patterned birefringent layer of the invention.

The patterned or patterned birefringent layer comprises a polymerized compound (I) or composition of the invention.

An optical component, system, or component creates, manipulates, or measures electromagnetic radiation.

An optoelectronic component, system or component operates by adjusting the optical properties of the material with an electric field. These are then related to the interaction between the electromagnetic (optical) and electrical (electronic) states of the material.

The invention further relates to an optical or optoelectronic component comprising a compound (I) or composition of the invention.

Preferably, the unpatterned or patterned optical or optoelectronic component can be used for, but not limited to, a waveguide, a security element or brand protection component, a bar code, an optical grating, a filter, a phase retardation film, a compensation film, a reflection Polarizing film, adsorption polarizing film, anisotropic scattering film compensation sheet and phase retardation film, torsional phase retardation film, cholesteric liquid crystal film, host guest liquid crystal film, monomer corrugated film, polarizer, piezoelectric cell, non-exhibition Linear optical properties of films, decorative optical components, brightness enhancement films, components for band selective compensation, components for multi-domain structural compensation, components for multi-view liquid crystal displays, achromatic phase retardation films, polarization state correction / Adjustment of components of membranes, optical or optical sensors, components of brightness enhancing films, components for optical base telecommunications components, patterned G/H-polarizers with anisotropic absorbers, patterned reflective circles Polarizer, patterned reflective linear polarizer, patterned MC (single corrugated film).

Preferred are security elements, particularly transmissive or reflective security elements; polarizers, compensating sheets and phase retarding films.

A further aspect of the invention provides an optical or optoelectronic component and multilayer system comprising a compound (I) or composition according to the invention.

Further, the present invention relates to a method for producing an optical or photovoltaic member comprising the compound (I) or composition of the present invention.

Preferably, the present invention also relates to an unpatterned or patterned optical or optoelectronic component according to the present invention as a phase retardation film and/or compensation film and/or a reflective polarizing film and/or an adsorption polarizing film for use in the following And / or the use of anisotropic scattering film:

(a) Twisted nematic (TN) liquid crystal display, hybrid array nematic (HAN) liquid crystal display, electrically controlled birefringence (ECB) liquid crystal display, super twisted nematic (STN) liquid crystal display, optical compensation type Refractive (OCB) liquid crystal display, π cell liquid crystal display, planar switching type (IPS) liquid crystal display, boundary electric field switching type (FFS) liquid crystal display, heavy direct alignment type (VA) liquid crystal display; all of the above display types are transmitted Or reflective or transflective mode applications;

(b) a display that produces a three-dimensional image or an image that changes with viewing angle;

(c) a security element or brand protection element;

(d) decorative optical components;

(e) a brightening film;

(f) an optical sensor;

(e) Optical base telecommunications components.

Moreover, it is preferred that the present invention be directed to a monomeric corrugated membrane.

Moreover, it is preferred that the invention be directed to many of the elements given above.

Yet another embodiment of the invention relates to an element comprising an optical or optoelectronic component, preferably a compensation film and a phase retardation film (angle of view, color shift, contrast, gray scale stability, brightness), which are used for: Components, such as transmissive and reflective security components; band-selective compensation: birefringence compensation film, which is patterned according to RGB (red, green, and blue), sub-pixels of the liquid crystal display to provide the final adaptation to the sub-pixel Compensating characteristics of the respective bands transmitted, compensation of multi-domain structures (such as transflective liquid crystal displays): birefringence compensation film with patterned characteristics according to the lateral variation characteristics of the components to be compensated, multi-view liquid crystal display Component: a compensation or phase retardation film that acts as a component of a display that provides different images for different viewing angles, a component of a three-dimensional liquid crystal display: a compensation or phase retardation film that is used as a component of a liquid crystal display that provides three-dimensional spatial image information. Chromatic phase retardation film: phase retardation film - compared to a simple colored phase retardation film - provides similar changes in the polarization state for use A wide range of wavelengths, such as the entire visible wavelength spectrum, polarized state correction / adjustment film: birefringent film, which is used to correct or adjust the polarization state, the goal is to activate the function or improve the performance of the optical component, optical or optical sensor Components, in particular polarizing sensitivity/selective sensors, components of brightness enhancing films, security element elements or decorative optical elements, components for optical base telecommunication elements, in particular polarized light based elements.

Yet another embodiment of the present invention is directed to an element comprising a patterned G/H-polarizer with an anisotropic absorber.

Preferably, the patterned G/H-polarizer with an anisotropic absorber is a film polarizer, a unit cell polarizer, a security element, or a decorative optical element.

Yet another embodiment of the present invention is directed to an element comprising a patterned reflective circular polarizer.

Preferably, the patterned reflective circular polarizer is a brightness enhancing film, a security element, or a decorative optical element.

Yet another embodiment of the present invention is directed to an element comprising a patterned reflective linear polarizer.

Preferably, the patterned reflective linear polarizer is a brightness enhancing film, a security element, or a decorative optical element.

Yet another embodiment of the present invention is directed to a beam steering element comprising an optical or optoelectronic component, preferably a compensation film and phase retardation film for a wavefront adjustment component.

Yet another embodiment of the present invention is directed to an element comprising a patterned MC (monomeric corrugated) film.

Preferably, the patterned monomer corrugated film is an anisotropic scattering film compensation film, an anisotropic reflection sheet, an antireflection film, a film having improved birefringence, a security element, or a decorative optical element.

Particularly preferred in the present invention are, for example, twisted nematic (TN) liquid crystal displays, hybrid aligned nematic (HAN) liquid crystal displays, electrically controlled birefringence (ECB) liquid crystal displays, Super twisted nematic (STN) liquid crystal display, optical compensation type birefringence (OCB) liquid crystal display, π cell liquid crystal display, planar switching type (IPS) liquid crystal display, boundary electric field switching type (FFS) liquid crystal display, and direct pair Quasi-type (VA) liquid crystal displays; all of the above display types are used in transmissive or reflective or transflective modes, which can be used to produce three-dimensional images or displays with varying viewing angles; beam steering components Optical base telecommunications components; optical sensors; many components.

In the present invention, novel compounds (I) and compositions have been discovered which exhibit a wide range of liquid crystal heats which have good adhesion properties to the substrate and the alignment surface. Moreover, these compounds can be obtained in a simple manner. This ease of use is extremely beneficial for a variety of applications.

Example:

Definition used in the examples

TAC=triethyl fluorenyl cellulose

LPP has the meaning of "linear photo-orientable polymer".

For the production of alignment layers, suitable LPP materials are described, for example, in the patent publications EP 0 611 786, WO 96/10049, and EP 0 763 552, and include cinnamic acid derivatives and ferulic acid derivatives. Things. For the following examples, the LPP materials described in U.S. Patent No. 156,107,427, and Example 4 were selected.

This photoalignment polymer is based on cinnamic acid ester as a photoreactive group. The polymer architecture of the photoalignment material is of the acrylate type.

CHN=cyclohexanone

CP=cyclopentanone

AD42=Irgacure 369,2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, available from BASF

AD282: Irgacure 907, 2-methyl-1[4-(methylthio)phenyl}-2-morpholine-propan-1-one

AD138: ginseng (2,4-di-tertiary-butylphenyl)phosphate available from Aldrich

AD184: Tego Flow 300, polyacrylate solution from EVONIK

AD43=BHT, 2,6-bis-tertiary butyl-4-methyl-phenol, available from Fluka

PP=polypropylene

K = crystal form

N = nematic phase

I = uniform phase

M = liquid crystal phase

(S _A )=single variable layer column A phase

Preparation Example 1:

1.1) Prepared by variant a) (XIII)

1.1.1) placed in a chemical reactor equipped with a stirrer, a thermometer and a separator for azeotropic removal of water during reflux, from 276.24 g of 4-hydroxybenzoic acid, 124.12 g of methylhydroquinone A mixture of 20.00 g of p-toluenesulfonic acid monohydrate and 1800 ml of o-xylene was heated to reflux in an oil bath at 178 °C. The separation of reflux and water started at a steam temperature of about 137 ° C for a total of 18 hours while separating about 35 ml of water. A pale yellow, slightly viscous suspension is formed. It was cooled to 65 ° C and 1250 ml of toluene was added. After further cooling to 25 ° C, the mixture was stirred at this temperature for 30 minutes and then filtered. The crystalline residue was washed with toluene to give a pale yellow solid. The orange filtrate was discarded. The solid was suspended in 1250 ml of ethyl acetate and stirred at 45 ° C for 1 hour. The suspension was cooled to 6 ° C, filtered, and the residue was washed with EtOAc (EtOAc) EtOAc (EtOAc). HPLC purity is 99% area

1.1.2) Filling a mixture of 156.76 g of 2-hydroxyethyl acrylate, 154.04 g of glutaric anhydride and 0.40 g of 2,6-di-tertiary-butyl-4-methyl-phenol to a mixer equipped with The thermometer is inside the chemical reactor. The mixture was heated to about 30 ° C and stirred until a homogeneous solution was obtained. Stop heating and add 4.725 ml of triethylamine. The exothermic reaction drives the temperature to rise to about 90 °C in 15 minutes. Cooling is carried out to maintain the temperature below 90 °C. After the exotherm was slowed, the reaction mixture was maintained at 75 °C for 2.5 hours and cooled to ambient temperature. A large amount of acid (XV) is obtained as a colorless, viscous liquid.

1.1.3.) placed in a chemical reactor equipped with a stirrer, thermometer and addition funnel, from 218.60 g bisphenol (XIV), 322.20 g acid (XV), 24.40 g 4. dimethylaminopyridine A mixture of 2.50 g of 2,6-di-tertiary butyl-p-cresol (BHT) and 1400 ml of toluene was cooled to +4 °C. A solution of 289.00 g of dicyclohexylcarbodiimide (DCC) dissolved in 500 ml of toluene was added over 1 hour to maintain the reaction temperature below +10 °C. The cooling unit was removed and the reaction mixture was stirred at room temperature (22-25 ° C) overnight (16 h). 1000 ml of a 5% aqueous solution of sodium hydrogencarbonate was added to the suspension, stirring was continued for 15 minutes, and then the mixture was filtered to remove precipitated DCC-urea. The two phase filtrate is separated and the lower aqueous phase is discarded. The toluene phase was washed once with 1000 ml of 10% sodium chloride solution, and the toluene was partially distilled off to yield about 825 g of a yellow solution. The solution was diluted with 825 ml of toluene to give a solids content of about 35%. The product was crystallized by slowly adding this solution to 4,720 ml of isopropanol and cooling to -10 °C. The suspension was stirred at -10 °C for 1 hour, filtered and the crystalline product was dried under vacuum at 25 °C to a fixed weight. The yield of the colorless crystalline product (XIII) was 470 g.

Analysis data:

HPLC purity: 93% area

Melting point: 5 °C

1.2) Prepared by variant b) (XIII)

1.2.1 Filling a mixture of 17.4 g of 2-hydroxyethyl acrylate, 17.1 g of glutaric anhydride and 0.05 g of 2,6-di-tertiary-butyl-4-methyl-phenol with a stirrer and a thermometer Inside the chemical reactor. THF 60 mL and 22 g of triethylamine were added to the mixture. The solution was heated to 50 ° C and stirred for two hours. The solution was cooled to -30 ° C and a mixture of 23 g of triethylamine and 18.9 g of methanesulfonyl chloride was added dropwise. After 1.5 h, 10.9 g of bisphenol (XIV) dissolved in 60 mL of tetrahydrofuran and 1.5 g of 4-dimethylaminopyridine were added to the mixture and stirred at room temperature (22-25 ° C) overnight (16 hours). The mixture was filtered through diatomaceous earth and silica gel. The solution was extracted with 200 mL of ethyl acetate and washed with 100 mL of HCl 0.5N and 100 mL of water. The organic phase was dehydrated with sodium sulfate and excess solvent was removed in vacuo. Purification on a chromatography column: SiO ₂ , hexanes / ethyl acetate 6/4 as a solvent to give 19 g of pale yellow oil. The product was crystallized by slowly adding 30 mL of ethanol to a solution prepared by dissolving 19 g of the product in 20 mL of ethyl acetate and cooling at -10 °C. The suspension was stirred at -10 °C for 1 hour, filtered and the crystalline product was dried in vacuo at 25 °C to a fixed weight. The yield of the colorless crystalline product (XIII) was 13.3 g. Analysis data:

HPLC purity: 96% area

Melting point: 5 °C

Mass Spectrum + EMS: 806.4 M NH ₄ ⁺

According to the synthesis of Example 1/Variation b), the compounds listed in Table 1 below were prepared, provided that they were prepared

-B1, 2-hydroxyethyl acrylate is substituted with 2-hydroxyethyl methacrylate and glutaric anhydride is replaced with maleic anhydride;

-B2, the glutaric anhydride is replaced by maleic anhydride;

-B3, 2-hydroxyethyl acrylate is substituted with 2-hydroxyethyl methacrylate and glutaric anhydride is replaced with maleic anhydride and the reaction methylsulfonium chloride is replaced with sulfinium chloride;

-B4, 2-hydroxyethyl acrylate is substituted with 2-hydroxypropyl acrylate;

-B5, 2-hydroxyethyl acrylate is substituted with 2-hydroxybutyl acrylate;

-B6, 2-hydroxyethyl acrylate is substituted with 4-hydroxybut-2-enyl acrylate;

-B7, 2-hydroxyethyl acrylate is substituted with 2-hydroxy-pentyl acrylate;

According to the synthesis of Example 1/Variation b), the compounds listed in Table 2 below were prepared, provided that they were prepared

-C1, the bisphenol (XIV) prepared according to the embodiment 1.1.1) is substituted with a bisphenol wherein L is hydrogen, and the starting material methylhydroquinone is substituted with hydroquinone;

At -C2, the bisphenol (XIV) prepared according to Example 1.1.1) is substituted with a bisphenol wherein L is a methoxy group, and the starting material methylhydroquinone is substituted with 2-methoxy-hydrogen.醌

Example 2:

Synthesis of single reactive compounds

According to the synthesis of Example 1/variation b), the compounds listed in Table 3 below were prepared, provided that they were prepared

-D3, bisphenol (XIV) is replaced by

It is prepared analogously to Example 1.1.1) from 4-hydroxybenzoic acid and 4-hydroxy-4'-cyano-biphenyl.

Application/Example 1a: Phase retardation film / quarter wave plate (on a TAC substrate with a hard outer cover)

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CHN have a 2% solids content). The wet film was dried at 80 ° C for 60 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 1)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

A 30% formulation in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibits uniaxial, uniform (=unpatterned, uniform birefringence across the entire film) anisotropy and no visible defects. The thickness of the crosslinked polymer film was finally 1310 nm. The film exhibits an optical phase retardation of 135 nm at 550 nm.

Application/Example 1b: Phase retardation film / quarter wave plate (on a TAC substrate with a hard outer cover)

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CHN have a 2% solids content). The wet film was dried at 80 ° C for 60 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 1)

95.4% of the compound synthesized in Example 1 (XIII)

4.0% AD282

0.5% AD184

0.1% AD43

A 30% formulation in a mixture of 80% DXG and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked by 1.5 J/cm ^{2 of} unpolarized UVA light in a large atmosphere. After this treatment, the film exhibits uniaxial, uniform (=unpatterned, uniform birefringence across the entire film) anisotropy and no visible defects. The thickness of the crosslinked LCP film was finally 1310 nm. The film exhibits an optical phase retardation of 135 nm at 550 nm.

Application/Example 2: Half-wave plate (on a TAC substrate with a hard outer cover)

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CHN have a 2% solids content). The wet film was dried at 80 ° C for 60 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 2)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

A 40% solution in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited uniaxial, uniform anisotropy and no visible defects. The thickness of the crosslinked polymer film was finally 2620 nm. The film exhibits a phase retardation of 270 nm at 550 nm. It is quite suitable for applications with one-half wave plates. Other intermediate phase retarders are also available.

Application/Embodiment 3: Security element (reflective)

A piece of 20 μm thick metallized PP foil was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution (by size 0) (by 80%) There is a 2% solids content in the solution of MEK and 20% CHN). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film is then exposed through a reticle to linearly polarized parallel UVB light (25 mJ/cm ² ; polarization azimuth Φ = 0°), followed by a directional mask Φ = 45° at 10 mJ/cm ² without a mask. exposure.

The sample is then coated with a k-bar (size 1)

98.4% of the synthesized (XIII) of Example 1.

1.0% AD42

0.5% AD184

0.1% AD43

A 30% solution in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited patterned uniaxial anisotropy and no visible defects. The crosslinked polymer film finally has a thickness of 1310 nm and exhibits a phase retardation of 135 nm at 550 nm. The optical axis of the birefringent film is oriented toward 0° by the reticle at the first exposure, and uniformly oriented along the 45° polarization azimuth in the subsequent exposure without the reticle.

When a polarizer is used to observe a sample, it is easy to see the pattern, depending on the position of the polarizer, showing a positive or negative image. This feature can be used for second level security elements.

Application/Embodiment 4: Safety Element (Transmissive)

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (There is a 2% solids content in a solution consisting of 80% MEK and 20% CHN). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film is then exposed through a reticle to linearly polarized parallel UVB light (25 mJ/cm ² ; polarization azimuth Φ = 0°), followed by a directional mask Φ = 45° at 10 mJ/cm ² without a mask. exposure.

The sample is then coated with a k-bar (size 1)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

A 40% solution in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited patterned uniaxial anisotropy and no visible defects. The thickness of the crosslinked birefringent film is finally 2610 nm. The film exhibits a phase retardation of 270 nm at 550 nm. The optical axis of the birefringent film is oriented toward 0° by the reticle at the first exposure, and uniformly oriented along the 45° polarization azimuth in the subsequent exposure without the reticle.

When the sample is observed with an orthogonal polarizer (transmission), the pattern is easily seen, depending on the orientation of the sample, showing a positive or negative image.

Application/Example 5: Cholesterol circular reflective layer

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CP have 2% solids dissolved). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 0)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

2% formulation in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited uniaxial, uniform anisotropy and no visible defects. The thickness of the crosslinked polymer film is finally about 50 nm.

The sample is then coated with a k-bar (size 2)

94.4% of the compound synthesized in Example 1 (XIII)

4.0% Lumogen S750 (available from BASF)

1.0% AD42

0.5% AD138

0.1% AD43

40% solution in MPK. The wet film was annealed at 50 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited a cholesterol orientation with the center of the reflection band at 620 nm and the width of the selective reflection band at about 40 nm. This layer looks uniform and has no visible defects. The thickness of the crosslinked cholesterol film eventually reached 2500 nm. The selective reflection zone is quite suitable for applications with circular reflective filters.

Application/Example 6a: Cholesterol circular polarizer

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CHN have a 2% solids content). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 1)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

A 30% solution in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited uniaxial, uniform anisotropy and no visible defects. The crosslinked polymer film finally has a thickness of 1310 nm and exhibits a phase retardation of 135 nm at 550 nm.

The sample is then coated with a k-bar (size 2)

94.4% of the compound synthesized in Example 1 (XIII)

4.0% Lumogen S750

1.0% AD42

0.5% AD138

0.1% AD43

40% solution in MPK. The wet film was annealed at 57 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited a cholesterol orientation, the center of the reflection band was at 615 nm and the selective reflection band width of the single cholesterol layer was about 40 nm. This layer looks uniform and has no visible defects. The thickness of the crosslinked cholesterol film eventually reached 2500 nm.

The combination of this quarter-wave plate and cholesteric membrane is quite suitable for circular polarizers in selective reflection zones.

Application / Example 6b: Cholesterol circular polarizer

A 40 micron thick TAC foil coated with a hard layer was corona treated (parameter: power = 0.3 kW; rotation speed 120 m/min; number of revolutions: 6) and then coated with L-bar solution with K-bar (size 0) (80% MEK and 20% CP have 2% solids dissolved). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (25 mJ/cm ² ).

The sample is then coated with a k-bar (size 0)

95.4% of the compound synthesized in Example 1 (XIII)

4.0% AD282

0.5% AD184

0.1% AD43

A 30% formulation in a mixture of 80% DXG and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked by 1.5 J/cm ^{2 of} unpolarized UVA light in a large atmosphere. After this treatment, the film exhibits uniaxial, uniform (=unpatterned, uniform birefringence across the entire film) anisotropy and no visible defects. The thickness of the crosslinked LCP film was finally 1310 nm. The film exhibits an optical phase retardation of 135 nm at 550 nm.

The sample is then coated with a k-bar (size 2)

94.7% of the compound synthesized in Example 1 (XIII)

4.0% Lumogen S750

4.0% AD282

0.2% AD138

0.1% AD43

Dissolve in 40% solution of 80% MEK and 20% DXG2. The wet film was annealed at 52 ° C and dried for 120 s and crosslinked by 1.5 J/cm ^{2 of} unpolarized UVA light in a large atmosphere. After this treatment, the film exhibited a cholesterol orientation, the center of the reflection band was at 615 nm and the selective reflection band width of the single cholesterol layer was about 40 nm. This layer looks uniform and has no visible defects. The thickness of the crosslinked cholesterol film eventually reached 2500 nm.

The combination of this quarter-wave plate and cholesteric membrane is quite suitable for circular polarizers in selective reflection zones.

Application/Example 7: Safety element on a PET substrate A piece of 20 micron thick PET foil was corona treated (parameter: power = 0.3 kW; rotational speed 120 m/min; number of revolutions: 6) and then with a K-bar ( Size 0) Coating LPP solution (2% solids content in a solution consisting of 80% MEK and 20% CHN). The wet film was dried at 80 ° C for 120 s; the dry film thickness was about 60 nm. The dry film was then exposed through a reticle to linearly polarized parallel UVB light (25 mJ/cm ² ; polarization azimuth Φ = 45° relative to the optical axis of the PET foil), followed by no photomask at 10 mJ/ Cm ^{2 is} exposed at a polarization azimuth angle Φ = -45°.

The sample is then coated with a k-bar (size 1)

98.4% of the compound synthesized in Example 1 (XIII)

1.0% AD42

0.5% AD184

0.1% AD43

A 30% solution in a mixture of 80% MEK and 20% CHN solvent. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited patterned uniaxial anisotropy and no visible defects. The thickness of the crosslinked birefringent film is finally 1310 nm and exhibits a phase retardation of 135 nm at 550 nm. The optical axis of the birefringent film is oriented parallel along the 45[deg.] polarization azimuth (the area covered by the reticle during the first exposure) and parallel to -45[deg.] (relative to the optical axis of the PET foil).

The sample is then coated with a k-bar (size 2)

94.4% of the compound synthesized in Example 1 (XIII)

4.0% Lumogen S750

1.0% AD42

0.5% AD138

0.1% AD43

40% solution in MPK. The wet film was annealed at 57 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited a cholesterol orientation with the center of the reflection band at 615 nm. This layer looks uniform and has no visible defects. The thickness of the crosslinked cholesterol film eventually reached 2500 nm.

Finally, a black film was obtained by using a commercially available black lacquer (Rayoflex manufactured by Sun Chemicals). It is excellent in adhesion to the cholesterol layer.

When the PET foil is observed with a polarizer, the sample (including a patterned quarter-wave plate and a cholesterol film) can be used as the second-level security element, which is shown as being masked depending on the orientation of the polarizer, respectively. Sexual and negative images. The first level color shift effect as a security feature is also shown.

Application / Example 8

A piece of 20 micron thick PET foil was corona treated (parameter: power = 0.3 kW; rotational speed 120 m/min; number of revolutions: 6).

The sample is then coated with a k-bar (size 2)

94.4% of the compound synthesized in Example 1 (XIII)

4.0% Lumogen S750

1.0% AD42

0.5% AD138

0.1% AD43

40% solution in MPK. The wet film was annealed at 57 ° C and dried for 120 s and crosslinked with 1 J/cm ^{2 of} unpolarized UVA light in nitrogen. After this treatment, the film exhibited a cholesterol orientation, the center of the reflection band was at 620 nm and the selective reflection band width of the single cholesterol layer was about 40 nm. This layer looks uniform and has no visible defects. The thickness of the crosslinked cholesterol film eventually reached 2500 nm. In addition, the film showed an unexpectedly good adhesion to the PET foil. The selective reflection zone is quite suitable for applications with circular reflective filters.

Application/Example 9 - Phase retardation film on a glass substrate The glass substrate was spin coated with an LPP solution (98% cyclopentanone dissolved in 2% solids content). The wet film was dried at 180 ° C for 10 s; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (120 mJ/cm ² ).

The sample was subsequently

67% Compound B2 (as described in Preparation Example 1.2.1)

30% LCP(1), 2,5-bis-[4-6-acryloyloxylhexyloxy)benzyl amyloxy]benzoic acid, available from ROLIC Technologies, Switzerland; Prepared in a reaction scheme 1, 2, 3, 4 similar to U.S. Patent No. 5,593,617.

1.0% AD42

1.0% AD18

1.0% AD43

The 20% formulation dissolved in aniline was spin coated. The wet film was annealed at 180 ° C and dried for 10 s and crosslinked by a 120 J/cm ² Hg lamp in nitrogen. After this treatment, the film exhibited a uniaxial uniform orientation with no visible defects. The thickness of the crosslinked film is finally 802 nm. The film exhibits a phase retardation of 105 nm at 550 nm.

Application/Example 10 - Phase retardation film on a glass substrate

Embodiment 10 is the same as Embodiment 9, provided that

- Compound B2 is substituted with compound B7 (as described in Preparation Example 1.2.1)

The thickness of the crosslinked film is finally 790 nm. The film exhibits a phase retardation of 89 nm at 550 nm.

Application/Example 11 - Phase retardation film on a glass substrate The glass substrate was spin coated with an LPP solution (98% cyclopentanone dissolved in 2% solids content). The wet film was dried at 180 ° C for 4 min; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (200 mJ/cm ² ).

The sample was subsequently

87.9% of the compound synthesized in Example 1 (XIII)

10% of the C2 synthesized in Example 1, Table 2

1.0% Irgacure 369

1.0% Tinuvin 123

0.1% BHT

The 20% formulation dissolved in aniline was spin coated. The wet film was annealed at 60 ° C and dried for 120 s and crosslinked by a 200 J/cm ² Hg lamp in nitrogen. After this treatment, the film exhibited a uniaxial uniform orientation with no visible defects. The thickness of the crosslinked film was finally 710 nm. The film exhibits a phase retardation of 84 nm at 550 nm.

Application/Example 12 - Phase retardation film on a glass substrate The glass substrate was spin coated with an LPP solution (98% cyclopentanone dissolved in 2% solids content). The wet film was dried at 180 ° C for 4 min; the dry film thickness was about 60 nm. The dry film was then exposed to linearly polarized parallel UVB light (200 mJ/cm ² ).

The sample was subsequently

87.9% of the compound synthesized in Example 1 (XIII)

10% Example 1, B6 synthesized in Table 1

1.0% Irgacure 369

1.0% Tinuvin 123

0.1% BHT

The 20% formulation dissolved in aniline was spin coated. The wet film was annealed at 73 ° C and dried for 120 s and crosslinked by a 200 J/cm ² Hg lamp in nitrogen. After this treatment, the film exhibited a uniaxial uniform orientation with no visible defects. The thickness of the crosslinked film is finally 760 nm. The film exhibits a phase retardation of 97 nm at 550 nm.

Claims (7)

A polymerizable liquid crystal compound (I) having a liquid crystal phase: the compound (1) is selected from the group consisting of compounds having the following chemical formula: Where R ¹ means: Wherein L is hydrogen or methoxy. According to the compound (I) of the first aspect of the patent application, it has an adhesiveness of >4. A liquid crystal composition comprising at least one compound (I) as described in the first item of the patent application. A method for producing an unpatterned or patterned birefringent layer, which comprises polymerizing the liquid crystal composition described in the compound (I) described in claim 1 or in the third paragraph of the patent application. A patterned or patterned birefringent layer comprising the compound (I) described in the first aspect of the polymerization application or the liquid crystal composition described in claim 3 of the patent application. A method for producing an optical or optoelectronic component comprising the compound (I) described in claim 1 or the liquid crystal composition described in claim 3 of the patent application. An optical or optoelectronic member comprising the compound (I) described in claim 1 or the liquid crystal composition described in claim 3 of the patent application.